Process for stabilization of protein textiles with 4-vinyl pyridine copolymers and products produced therefrom



United States Patent PROCESS FOR ST ABILIZATIGN OF PROTEIN TEX- TILES' WITH 4-VINYL PYRlDlNE COPGLYMERS AND PRODUCTS PRODUCED THEREFROM Benjamin B.. Kine and Nathaniel A. Matlin, Levittown, Pa., assignors toRohm & Haas Company, Phiiadeiphia, Pa., a corporation ofDelaware No Drawing. Application March 22, 1954 Serial No: 417,977

20 Claims. (Cl. 8--127.6)

This invention relates=to%the' treatment ofv protein=containing textile materials and: to the products thereof. It relates moreparticularly to a process of treating textile materials comprising scale-surfaced protein fibers, such as wool: and wool-containing fabric, whereby the textile materials are stabilized against shrinking and felting.

An object of this invention is to provide aqueous dispersions of resins which are so stable that they can be stored and shipped,.and which, when they are appliedto protein-containing. textile materials and are then heated, markedly reduce the tendency of the materials to shrink or. render them substantially shrink-proof. Another object is to provide a process for shrink-proofing and felt-proofing textiles containing scale-surfaced protein-fibers, whetherof natural or artificial origin, through theuse of the aforesaid dispersions. It is: anobject'to shrink-proof and felt-proof thetextileswithoutadversely affecting such otherv properties of the textile as wearing qualities, tensile strength, or. hand. Still another object is to produce protein=coni taining textile materials; particularly woolen fabrics, which have a much reduced tendency to shrink and which alsoretain the desirable characteristics which are associated with woolen fabrics.

While thisinvention is principally concerned with im', provements of, and more particularly the reduction of shrinkage and/or complete stabilization of textile materials of proteinaceous types, and while the invention is described primarily interms of wool-containing textiles, the invention. embraces. the treatment of other proteincontaining textile materials, such as those made of or containing silk, mohair, fur, Aralac (casein) and other synthetic fibers which are produced from ca'sein,-soybeans, collagen, et cetera, and especially scale-surfaced protein fibers of either natural or artificial origin. The terms textile and: textile materials are used herein to include filaments, fibers, yarns, threads, plied yarns, rovings, and slivers as such or in woven, knitted, felted or otherwise formed fabrics, sheets, cloths and the like. Such textile materials may contain only one kind of proteinaceous fiber or'a mixture of such fiberswith other natural or synthetic fibers such as of cotton, linen, rayon, nylon, or polymers of acrylonitrile.

A- number of different methods have been proposed for the treatment of textile materials formed of" or containing wool or other protein fibers inorder' to prevent or decrease felting and shrinking. In many cases; such reduction. in. felting" and shrinking tendencies: has been obtained at the'sacrificeof some other desirable property of thematerial. Some treatments-damage the fiber' and reduce the wearing qualities while others impart afl'unde sirabl'e: harshness to the fabric; Other treatments are not-permanently effective and may even cause an ultimate increase in shrinkage. Still other shrink-proofing methods are difiicult to apply with uniformity and createhazards to the workers involved in their applications.

Certain polymers of the linear type have alsobeen recommended, such as' those containing isocyanate' groups and certainv esters of acrylic or methacrylic acid; such as the glycidylesters thereof. The types of polymers of this class thatihave been found effective for reducing the shrinkage and-felting of: protein-containing textiles have so far beenii of rather limited scope. Ithas' be'enfound that many polymers of this type, which are quite similar to those which are. effective, have no effect or'ha've so little effect as tobe of no practical value.- For example, polymers or copolymers of glyceryl methacrylate',

CH C (CH COOCH CH( OH) CH OH are of. this character.

The process of treating'thetextile materialsin accordance with the invention comprises-impregnating them with an-aqueous dispersion of the kinddescribed in detail below and then heating the textilesata temperature which is at least as highas 212 F., but which is lower than the'charring pointof the textile. During the treatment of the textiles in this=way achemical reaction is believed to takeplace. between the: proteinaceous portion of the textile and: thecopolymer in the. dispersion. The copolymer appearsto: be. chemically bound to the textile and not merely depositedasa dry coating on the fibers. As a result, the resinoustcopolymer' is not leached'or removed from the textile during; subsequentwet-washing. or drycleaning operations.

In accordance with: the presentinvention, it has been found that the application to textiles containing protein aceousfibers or filaments of'an aqueous dispersion of a water insoluble linear copolymer of atleast 3% by Weight of 4-vinyl pyridine with at least one other copolymerizable monoethylenicallyunsaturated monomer improves the abrasion resistance of the textiles and is highly effective for the reduction of shrinkage and felting and/or forv the substantially complete stabilization against. washing on laundering of textiles comprising scale-surfaced protein fibers; such as wool.

lthas-been found that 4-vinyl pyridine is unique among the various vinyl pyridines in forming copolymers which are capable of reducing shrinkage and felting of fabrics containing scale-surfaced protein fibers? or filaments, such as wool. Similar insoluble copolymers: of 2-vinyl pyridine, Z-methyl-S-vinyl pyridine an'dS-methyl-Z-vinyl pyridinehave been foundto have little or no'elfectin reducing shrinkage of wool fabrics.

The-copolymers must not be-Water-soluble- The upper limit of the 4-vinyl pyridine component in the copolymer molecule depends. on the nature of the como'nomer or comonorners in the particular copolymer. When the comonomer isof a highly insolubletype, a-larger proportion, suchas up to of the 4-vinyl. pyridine, may be combined in the copolymer. The 4-vinyl pyridine may becopolymerized with a mixture of'comonomers, one of solubilizing type and the other of insolubilizing type in which eventthe proportion of 4-vinyl pyridine must be reduced in direct proportion to the amount of solubilizing comonomer introduced. For mostpurposes, copolymers containingfrom 3' to 30% by weight of 4-vinyl pyridine with at least one insolubilizingcomonomer are quite practicalfrom the standpoints ofcost and-controlling properties inthe-treatedtextile, such as. hand.

Other polymerizable compounds containing a single ethylenically unsaturated group that may becopolymerized with the 4-vinyl pyridine to produce binary, ternary,.etc. copolymers include the estersofacrylic. acid or methacrylic acid with monohydric alcohols such as methyl, ethyl, butyl, octyl, dbdecylLcyclohexyl, cyanoethyl, benzyl, phenylethyl, and the like; diesters ofitaconic acid and the. above. alcohols; esters of maleic, fumaric or citraconic acids, and the above alcohols; vinyl esters ofcarhoxylic acid's'such as acetic; propionic,

' butyric, and the like; vinyloxyalkyl esters such as vinyloxyethyl acetate, etc.; vinyl ethers such as ethyl vinyl ether, butyl vinyl ether,'octyl vinyl ether; methacrylonitrile or' acrylonitrile; acrylamide,',or methacrylamide, and N-alkyl-substituted ,amides of these types; vinyltoluene, vinylnaphthalenes, such as 4-chloro-1-vinylnaphthalene, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene fiuoride,.viuylidene cyanide, l-chlorol-fluoroethylene, ethylene, and styrene. 1

The emulsifiers or dispersingagents that may be used for preparing the monomeric emulsions before copolymerization or dispersions of. the polymer after polymerization include those of anionicand non-ionic types. In some cases, it is preferable to use a mixture of anionic and non-ionic emulsifying and dispersing agents. Suitable anionic agents include the sulfates ofjhigher fatty alcohols and their alkali 'metal salts, such as sodium lauryl sulfate; aryl and/or alkyl substituted phenol sul-- fonates; sulfonated alkyl phenoxyethoxyethanols having from 1 to 5 oxycthylene units'per molecule; sulfonated higher alkyl'succinates, such as di-t-octyl sodium sulfosuccinate; suitable non-ionic agents, such as alkylphenoxypolyethoxyethanols having alkyl groups of about seven to eighteen carbon atoms and 6 to 60 or more oxyethylene units, such as heptylphenoxypolyethoxyethanols, octylphenoxypolyethoxyethanols, methyloctylphenoxypolyethoxyethanols, nonylphenoxypolyethoxyethanols,. dodecylpheuoxypolyethoxyethanols, and the like; polyethoxyethanol derivatives of methylene linked alkyl phenols; sulfur-containing agents such as those made by condensing 6 to 60 or more 'moles of ethylene oxide with nonyl, dodecyl, tetradecyl, t-dodecyl, and the like mercaptans or with ialkylthiophenols having alkyl groups of six to fifteen carbon atoms; ethylene oxide derivatives of long-chained carboxylic acids, such as lauric, myristic, palmitic, oleic, and the like or mixsolution of an alkali metal hydroxide, such as sodium 1 temperature and the concentration of 'the caustic hydroxide solution. Instead of relying on hydrolysis to introduce the carboxyl groups, the appropriate amount of acrylic acid, methacrylic acid, itaconic acid or other polymerizable acid, such as maleic, fumaric and citraconic, may be directly introduced into the emulsified mixture of monomers so that it is copolymerized with the 4-vinyl pyridine and other proportion. V

The polymerizable emulsions can be prepared at temperatures from 0 C. to about-100 C., but intermediate temperatures are much preferred. Thus, when the preferred copolymers with esters are made with the esters in which the alkyl group contains one to four carbon atoms, a temperature from about 10- C. to about 60 C. is employed, whereas a higher temperature, e. g., C. to 80 C., isrecommended when; esters containing five to eight carbon atoms in the alkyl group .are copolymerized. Peroxidic free-radical catalysts, particularly catalytic systems oftheredox type, are recommended.

' Such systems, as is well known, are combinations of tures of acids such as found in tall oil containing 6 to 60 oxyethylene units per molecule; analogous ethylene oxide' condensates of long-chained alcohols, such as octyl, decyl, lauryl, or cetyl alcohols, ethylene oxide derivatives of etherified or esterified polyhydroxy compounds having a hydrophobic hydrocarbon chain, such as'sorbitan monostearate containing 6'to 60 oxyethylene units, etc.; also ethylene oxide condensates of long-chain or branched-chain amines, such as dodecylamine, hexadecylamine, and octadecylamine, containing 6 to 60 oxyethylene groups, block copolymers of ethylene oxide and propylene oxide comprising a hydrophobic propylene oxide section combined with one or more hydrophilic ethylene oxide sections.

Particularly valuable dispersions are obtained by emulsifying a mixture of 4-vinyl pyridine and one or more monomeric esters of acrylic, inethacrylic, or itaconic acid or mixtures of these acids in water and polymerizing the mixture while it is in the'emulsified form. The monomeric esters which have proven to be most satisfactory are the alkyl esters in which the alkyl group contains one to eight carbon atoms and which are exemplified by the following: methyl, ethyl, n-propyl, iso propyl, n-butyl, isobutyl, sec-b'utyl, tert-butyl, isoamyl, tert-amyl, hexyl, heptyl, n octyl, and2-ethylhexyl acrylates, methacrylates, and itaconates. Toimpart alcoholcompatibility, a portion of the ester component may be hydrolyzed to" the free acid and converted to the ammonium, sodium, potassium, or'lithium salt by means of the corresponding hydroxide. Hydrolysis may be suffi cient to produce from as little as /2% by weight of carboxyl-containing (--CQOH)v monomeric units in the copolymer to as much as 5% to 10% of carboxylicacid units in the copolymer, but generally 1% to 2% ,is

preferred. 7 1

Hydrolysis of the 4-v'inylpyridine/ester-copolymer may be elfected by either acid or alkaline treatments. Preferably, the copolymer is treated with an aqueous oxidizing agents and reducing agents such as a combination of potassium persulfate and sodium metabisulfite. Other suitable peroxidic agents include the per-salts such as the alkali metal and ammonium persulfates and perborates, hydrogen peroxide, organic hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide, and esters such as tert-butyl perbenzoate. Other reducing agents include water-soluble thiosulfates, hydrosulfites, tertiary amines, such as triethanolamine, and the salts, such as the sulfates, of metals which are capable of existing in more than one valence state, such as cobalt, iron, nickel, and copper. 'The most convenient method of preparing the dispersion of copolymers comprises agitating an aqueoussuspension or emulsion of a mixture of copolymerizable monomers and a redox catalytic combination at room temperature without the application of external heat. The amount of catalyst can vary but for purposes of efiiciency' from 0.01% to 3.0%, based on the weightv of the monomers, of the peroxidic agent and the same or lower proportions of the'reducing agent are recommended. In this way, it is possible to prepare dispersions which contain as little as 1% and as much as 60% or even more of the resinous copolymer on"aweight basis. It is, however, more practical, and hence preferred, to produce dispersions which contain about 30-50% resin-solids;

The proportion of the copolymer that is applied to the fabric may vary widely, such as from 1% to 20%, by weight of the fabric, a proportion of 1% to 7 /2 being preferred. The hand or feel of the fabric may be varied widely depending on the comonomer o1- cornonomers selected. Thus, a'softer and more lubricous'hand may be imparted by copolymerizing the 4-vinyl pyridine with a comonomer that introduces'a long-chain fatty group into the copolymer. For example, the '4-vinyl pyridine'may be'copolymerized' with acrylic, methacrylic, or itaconic esters of alcohols containing from 1 to 18 carbon atoms, the longer the chain of the alcohol, the more lubricous thehand.

The dispersionis deposited-on the textile material by such 'meansas exhausting,'spraying, padding, or dipping. What is required is that the textile material be saturated and impregnated by the dispersion This canbe done at any desired temperature short of the boiling point of monomer in the desired being treated mustpick. up. or. takes up and. then. retain sufficient dispersions to providefiom. 1% to ab.out.20%, and preferably. from 1 /2 to..7. /&.%. of" the copolymer, based on the weight .ofthe dry. textile.

The impregnated. textile-material. must then beheated at a temperature between 212' F and 700 FL for. a period of about ten seconds to 30 minutes, the higher the temperature, the shorter the period required. In any event the time and temperatureshould not be such :as to damage the fabric. Preferably this heating is effected at a temperature from 240 F; (for about 1015 minutes) to about 310 F. (for about 5-10 minutes), audit is believedthat it effects some chemical reaction. involvingthe polymer and possibly the textile. In any event, the heating. sets the polymer on the textile, and, in the case of-wool, reduces shrinkage and/or impartsfull dimensional stability thereto. Drying of the treated textile. and the heat-treatment which effects the chemical reaction can be carried out simultaneously or concurrently in one step, or the textile can be substantially or completely dried at a conveniently lower temperature and then heated later at the. higher temperature. As will be evident to those skilled inthe art, the optimal length of the heating period depends on the particular temperature which is employed, on the particular copolymer, and on the quantity thereof which is on the textile. But in any case, the heat-treatment does not require a long period and is usually measured in minutes, generally one to thirty minutes and preferably about five to fifteen minutes. The most satisfactory time of heating for any particular combination of dispersions andtextile is readily determined by heating pieces of the impregnated textile for varying lengthsof time at a given temperature and then measuring the resultant stabilization of the individual pieces by means of a wet-washing test.

In some cases, it may be advantageous to add an acid to the dispersion with which the textile is treated to accelerate the reaction and to bring about the stabilization or reduction in shrinkage in a shorter period of time at a given temperature or at a lower temperature in a given time. Strong acids such as formic, oxalic, sulfuric, and phosphoric acids are recommended. For this purpose, from 1% to 2% acid, based on-the weight of the pad liquor, is suggested. It has also been found that the use in conjunction with the dispersions of such acid catalyst with an auxiliary reactive substance, such as formaldehyde, ormaterials which are equivalents of formaldehyde, suchas glyoxal or formals, or mixtures of formaldehyde or the like with aminoplast-forming compounds, or lowmolecular weight, water-soluble, reaction products, preferably of formaldehyde or the like with such compounds,

enhances the stabilization of woolen or proteinaceous textiles. While such auxiliary reactive substances and the acid catalyst may be employed as an added component of'the dispersions, they may also be employed by applying a solution of the auxiliary reactive substance and'the acid catalystafter the textile has been treated with the dispersion. The use of the auxiliary reactive substance is advantageous in some cases'where it becomes especially evident on extended laundering of the textile. Also in combination fabrics, such as those containing fibers or yarns of silk or cellulosic type, such as cotton or rayon, as well as fibers or-yarns of'proteinaceous'types,

.urea, N,N'-dimethylurea, N,N'-diethylurea, N,N-dimethoxymethylurea, N,N-dimethoxymethylurea, N,N'-dieth- ,oxyethylurea, tetramethoxymethylurea, tetraethoxyethyl- 5 urea. Similar reaction products of formaldehyde with triazines, sucli as melamine may also be employed, such as N,N-dimethylmelamine and alcohol-modified melamine-formaldehyde thermosetting resin condensates, e. g., of methyl and ethyl alcohols, for example, dimethoxymethyl-monomethylolmelamine.

The treated textiles are characterized by greater resistance to abrasion and/or reduced shrinkage and, in many cases, fully practical dimensional stability against laundering, by which is meantthat they are substantially shrink-proof. They do not-stiffen, degrade or discolor on ageing or on exposure to ultraviolet light as do'comparable textiles which have been treated, for example, with latices of butadiene copolymers.

Thev effectiveness of the dispersions exemplified below in stabilizing wool was determined by impregnating measuredpiecesof flannel with them, drying, and heating'the impregnated piecesof flannel .at a-temperature of 240 F. orhigher, laundering, the piecesin hot water, then drying them and measuring the shrinkage. In these tests pieces of woolen flannel (2/2 right hand 45 twill, 55 x 44; S-twist in Warp ends, Z-twist in the filling; scoured,.carbonized; neutralized and bleached) were used. All pieces were 10'inches'square,.with axes along the yarn systems. The pieces of. flannel were paddedwith a pad liquor of the resin dispersion which was so adjusted in solidscontent as to" provide the desired'amount of'resins-solids (1%-20% based on the weight of the dry flannel) at a pick-up of about 75%;.that1 is, when the flannel contained the emulsion in an amount equal to about 75% of the weight ofthe dry flannel. The treated specimens were driedand heated and cured at a temperature of at least 240 F; The specimenswere washed, together. with untreatedpieces of flannel, in a Cascade wheel'washer. con taining 70 grams oflsoap (Ivory) in 10' gallons of. water for five hours. In all cases the load in. the washer was made up to three pounds with cotton toweling and the temperature was. maintained at 140" F. The, values of shrinkage are given as percentage reduction inthe initial area' after taking into account any inherent residual shrinkage in the initial fabric that may be present as a result of previous drying under tension and is removable by simply wetting and drying. In other Words; the shrinkage valueshereinbelow are obtained by subtracting relaxation shrinkage from theactual shrinkage measured.

The following examples serve to illustratethis invention:

Ei'camplal A dispersion of a copolymer was prepared by emulsifying parts by weight of n-butyl acrylate with 10 parts by weight'of 4-vinyl pyridine in about 300 parts by weight of water with about 6 parts by weight of an-ethylene oxide-condensation product of'an octyl phenol containing between 30 and 50 oxyethylene units per molecule. To the emulsified-monomers 0.3% by weight (on the total weight of monomers) of ammonium persulfate, 1.0% of triethanolamine, and 0.06% of sodium hydrosulfite were added to catalyze the copolymerization which was carried out for a period of seventeen minutes. During this period the temperature rose from 20 C. to 46C.

The resin dispersion was diluted to a 13.5% concentration of the resin (copolymer) content and applied'to a wool flannel as described above; After drying 10 minutes at 240 F., followed by curing for 10 minutes at 300 F., it was found that the proportion of copolymer applied-to the fabric was about 10.0% of the weight of the fabric. The shrinkage of the treated fabric after'the five-hour wash described hereinabove was zero.

Example. 2.

The-procedurexof Example 1 was followed'except that after dryingthe-fabrictat 240? (3., it was passedzthrough an aqueous solution containing 1%Z-sulfuric: acid and: 1% formaldehyde and then dried 10 minutes at 240 C. and curedfor a period of 10 minutes at 300 F. The result- 7 Example 3 The procedure'of Example 1 was followed except that the dispersion was diluted to 2 /2% copolymerconcentration before application so that,-1 /z% wasrtaken up by the fabric. The fabric showed 2% shrinkage on completion of the five-hour wash test 7 g V I 7 Example! I V The proce dure of Example 3'was followed except that after drying the fabric at 240 F., it was passed through a 3% aqueous solution of .dimethoxymethylurea and cured for a period of minutes at 300 F. The fabric showed no shrinkage as a result of the five-hour wash test. 7 i 7 Example The procedure of Example 1 was followed with a copolymer obtained by emulsion polymerization of 94.5% n-butyl acrylate, 0.5% methacrylic-acid, and 5% 4-vinyl pyridineand neutralization with ammonium hydroxide. The treated fabric showed. no shrinkage on completion of the five-hour wash test. V I

Example 6 2 Example 7 The procedure of Example 1 is followed with a copolymer of 85% diethyl itaconate and of 4-vinyl pyridine. The fabric shows no shrinkage on completion of the wash test.

Example"8 The procedure of Example 1 is followed with a copolymer of 75% of'n-octyl acrylate with 25% of 4- vinyl pyridine.

The fabric exhibits no shrinkage as a result of the five-hour wash test.

Itis to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

We claim: 7

1. A process for treating protein textile materials to reduce the shrinkage thereof comprising impregnating a protein textile material with an aqueous dispersion containing 1 to of a water-insoluble, linear copolymer' of 3 to 70% by weight of 4-vinyl pyridine and 97 to 30% respectively of comonomeric material consisting of at least one member selected from the group consisting of (1) esters of an acid selected from the group consisting of acrylic, methacrylic, itaconic, maleic, fumaric, and citraconic acids and a monohydric alcohol selected from ,the group consisting of acyclic alkanols having 1 to 18 carbon atoms, cyclohexanol, cyanoethanol, benzyl alcohol, and phenylethyl alcohol, (2) vinyl esters of fatty acids having 2 to 4 carbon atoms, (3) vinyloxyethyl acetate, (4) alkyl vinyl ethers in which the alkyl group has 2 to 8 carbon. atoms, methacrylonitrile,'acrylonitrile, acrylamide, methacrylamide, vinyltoluene, 4-chloro-1-vinylnaphthalene, vinyl bromide, vinyl chloride, vinyiidene chloride,vinylidenefiuoride, vinylidenecyanide, l-chlorol-fiuoroethylene, ethylene, and styrene, at least sufiicient of the comonomeric material being of water-insolubilizing character to render the copolymer water-insoluble, and subsequently heating the impregnated textile to atemperature of 212? to 700 F. until the fabric shows substantial reduction-ofshrinkage on laundering. 7

2 A processffor treating protein textile materials to reduce the shrinkage thereof comprising impregnating a protein textile material with an aqueousdispersion containing 1 to' 20% ,of a water-insoluble, linear 'copolymer of 3 to by weight of 4-vinyl pyridineiand97' to 30% respectively of at 'leas'tone ester of'acrylic acid and an acyclic alkanol having 1 to 18 carbon atoms, and'subsequentlyheating theimpregnated textile to a temperature of 212 to 700}: F. unti1 the fabric shows substantial reduction of, shrinkage ,on laundering.

3. A process for treating protein textile materials. to reduce theshrinkage thereof comprising impregnatinga protein textile material'with an aqueous dispersion containing 1 to 20% 'of a water-insoluble, linear copolymer of 3 to 70% by weight ofA-vinyl pyridine, about /z% to 5% of methacrylic acid, and 96 /2 to 30% respectively of at least one, ester of'acrylic acid with an acyclic alkanol having 1 to 18 carbon atoms, and subsequently heating the impregnated textile to a temperature of 212 to 700 F. unti1 the fabric shows substantial reduction of shrinkage onlaundering. a I

4. A process for treatingprotein textile materials to reduce the shrinkage thereof comprising impregnating a protein textile material with an aqueous dispersion containing 1 to 20% of a water-insoluble, linear copolymer of 3 to 70% by Weight of 4-vinyl pyridine, about /2.% to 5% of acrylic acid, and 96% to 30% respectively of at least one ester of acrylic acid with an acyclic alkanol having 110 18 carbon atoms, and subsequently heating the impregnated textile to a temperature of 212 to 700 F. until the fabric shows substantial reduction of shrinkleast one ester of acrylic acidwith an acyclic alkanol having 1 to 18 carbon atoms, and subsequently heating the impregnated textile to a temperature of 212 to 700 F. until the fabric shows substantial reduction of shrinkage on laundering.

6. The process as defined in claim 1 in whichthe copolymer comprises 5% 4-vinyl pyridine and 95% n-butyl acrylateJ 7. The process as defined in claim 1 in which'the copolymer comprises about 5% 4-vinyl pyridine, about /2% methacrylic acid, and about 94.5 n-butyl acrylate.

8. The process as defined in claim 1 in which the copolymer comprises about i 5% 4-vinyl pyridine, about 2% acrylic acid, and about 93% n-butyl acrylate.

9. The process as defined in claim 1 in whichthe co- -polymer comprises 15% 4-vinyl pyridine and diethyl itaconate.

10. 'The process as defined in claim 1 in which the co-.

containing protein fibers stabilized against shrinkage on laundering, said material being the product of the process of claim 2.

13. As an article of manufacture, a textile material containing wool fibersstabil-ized against shrinkage oh laundering, said material being the product of the process of claim 1.

14. As an article of manufacture, a textile material containing wool fibers stabilized against shrinkage on laundering, said material being the product of the procesof claim 2.

15. As an article of manufacture, a textile material containing wool fibers stabilized against shrinkage on laundering, said material being the product of the process of claim 3.

16. As an article of manufacture, a textile material containing wool fibers stabilized against shrinkage on laundering, said material being the product of the process of claim 6.

17. As an article of manufacture, a textile material containing wool fibers stabilized against shrinkage on laundering, said material being the product of the process of claim 7.

18. As an article of manufacture, a textile material containing Wool fibers stabilized against shrinkage on laundering, said material being the product of the process of claim 8.

19. As an article of manufacture, a textile material containing wool fibers stabilized against shrinkage on laundering, said material being the product of the process of claim 9.

20. As an article of manufacture, a textile material containing wool fibers stabilized against shrinkage on laundering, said material being the product of the process of claim 10.

References Cited in the file of this patent UNITED STATES PATENTS 2,138,763 Graves Nov. 29, 1938 2,332,817 Smith Oct. 26, 1943 2,406,412 Speakman et al. Aug. 27, 1946 2,411,899 Semegen Dec. 3, 1946 2,468,716 Nyquist Apr. 26, 1949 2,499,653 Kropa et al. Mar. 7, 1950 2,637,717 Basdekis May 5, 1953 2,694,696 Melamed Nov. 16, 1954 FOREIGN PATENTS 611,828 Great Britain Nov. 4, 1954 

1. A PROCESS FOR TREATING PROTEIN TEXTILE MATERIALS TO REDUCE THE SHRINKAGE THEREOF COMPRISING IMPREGNATING A PROTEIN TEXTILE MATERIAL WITH AN AQUEOUS DISPERSION CONTAINING 1 TO 20% OF WATER-INSOLUBLE, LINEAR COPOLYMER OF 3 TO 70% BY WEIGHT OF 4-VINYL PYRIDINE AND 97 TO 30% RESPECTIVELY OF COMONOMERIC MATERIAL CONSISTING OF AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF (1) ESTERS OF AN ACID SELECTED FROM THE GROUP CONSISTING OF ACRYLIC, METHACRYLIC, ITACONIC, MALEIC, FURARIC, AND CITRACONIC ACIDS AND A MONOHYDRIC ALCOHOL SELECTED FROM THE GROUP CONSISTING OF ACYCLIC ALKANOLS HAVING 1 TO 18 CARBON ATOMS, CYCLOHEXANOL, CYANEOTHENOL, BENZYL ALCOHOL, AND PHENYLETHYL ALCOHOL, (2) VINYL ESTERS OF FATTY ACIDS HAVING 2 TO 4 CARBON ATOMS, (3) VINYLOXETHYL ACETATE, (4) ALKYL VINYL ESTERS IN WHICH THE ALKYL GROUP HAS 2 TO 8 CARBON ATOMS, METHACRYLONITRILE, ACRYLONITRILE, ACRYAMIDE, METHACRYLAMIDE, VINYLTOLUENE, 4-CHLORO-1-VINYLNAPHTHALENE, VINYL BROMIDE, VINYL CHLORIDE, VINYLIDENE CHLORIDE, VINYLIDENE FLUORIDE, VINYLIDENE CYANIDE, 1-CHLORO1-FLUOROETHYLENE, ETHYLENE, AND STYRENE, AT LEAST SUFFICIENT OF THE COMONOMERIC MATERIAL BEING OF WATER-INSOBULIZING CHARACTER TO RENDER THE COPOLYMER WAER-INSOLUBLE, AND SUBSEQUENTLY HEATING THE IMPREGNATED TEXTILE TO A TEMPERATURE OF 212* TO 700*F. UNTIL THE FABRIC SHOWS SUBSTANTIAL REDUCTION OF SHRINKAGE ON LAUNDERING. 